Water and oil repellency treatment of fibre product

ABSTRACT

A textile having excellent water- and oil-repellency can be obtained by a method of preparing a treated textile, having steps of: (1) preparing a treatment liquid comprising a water- and oil-repellent agent, (2) adjusting pH of the treatment liquid to at most 7, preferably at most 3, (3) applying the treatment liquid to a textile, (4) treating the textile with steam, and (5) washing the textile with water and dehydrating the textile, wherein the water- and oil-repellent agent is at least one fluorine-containing compound selected from the group consisting of a fluorine-containing polymer and a fluorine-containing low molecular weight compound, and the water- and oil-repellent agent or the treatment liquid contains an organic salt.

FIELD OF THE INVENTION

[0001] The present invention relates to a treatment for impartingexcellent water repellency and oil repellency to a textile. A method ofthe present invention is particularly useful for a carpet.

BACKGROUND OF THE INVENTION

[0002] Hitherto, various treatment methods have been proposed in orderto impart water repellency, oil repellency and soil releasability to atextile such as a carpet. For example, a process (hereinafter, sometimesreferred to as “Exhaust process”) of treating a textile comprisingdecreasing a pH of a treatment liquid, applying the treatment liquid tothe textile, thermally treating the textile with steam, washing thetextile with water, and dehydrating the textile is proposed.

[0003] A method comprising the Exhaust process is proposed in U.S. Pat.Nos. 5,073,442, 5,520,962 and 5,516,337 and International Publication WO98/50619.

[0004] U.S. Pat. No. 5,073,442 discloses a method of treating a textile,comprising conducting an Exhaust process by using a water- andoil-repellent agent comprising a fluorine-containing compound, aformaldehyde condensation product and an acrylic polymer. U.S. Pat. No.5,520,962 discloses a method of treating a carpet, comprising conductingan Exhaust process by using a fluorine-containing compound and apolymeric binder. U.S. Pat. No. 5,516,337 discloses a method of treatinga textile, comprising conducting an Exhaust process by using afluorine-containing water- and oil-repellent agent and a metal compoundsuch as aluminum sulfate. International Publication WO 98/50619discloses a method of treating a carpet, comprising conducting anExhaust process by using a fluorine-containing water- and oil-repellentagent and a salt such as a magnesium salt.

[0005] When these methods are used to conduct the Exhaust process,sufficient water-repellency, oil-repellency and soil releasability havenot been obtained.

SUMMARY OF THE INVENTION

[0006] An object of the present invention is to give a textile excellentin water repellency and oil repellency, when an Exhaust process is used.

[0007] The present invention provides a method of preparing a treatedtextile, comprising steps of:

[0008] (1) preparing a treatment liquid comprising a water- andoil-repellent agent,

[0009] (2) adjusting pH of the treatment liquid to at most 7,

[0010] (3) applying the treatment liquid to a textile,

[0011] (4) treating the textile with steam, and

[0012] (5) washing the textile with water and dehydrating the textile,

[0013] wherein the water- and oil-repellent agent comprises at least onefluorine-containing compound selected from the group consisting of afluorine-containing polymer and a fluorine-containing low molecularweight compound, and the water- and oil-repellent agent or the treatmentliquid contains an organic salt.

[0014] The present invention also provides a textile prepared by theabove-mentioned method and a water- and oil-repellent agent used in theabove-mentioned method.

DETAILED DESCRIPRION OF THE INVENTION

[0015] The procedure used in the present invention is an Exhaust processwhich comprises decreasing pH of a treatment liquid comprising afluorine-containing compound, applying a treatment liquid to a textile,thermally treating the textile, washing the textile with water, anddehydrating the textile.

[0016] In the step (1) of the method of the present invention, thetreatment liquid comprising the water- and oil-repellent agent, which isapplied to the textile, is prepared. The treatment liquid comprising thewater- and oil-repellent agent may be in the form of a solution or anemulsion, particularly an aqueous emulsion. The water- and oil-repellentagent before the preparation of the treatment liquid may contain theorganic salt, or the treatment liquid may be prepared by adding theorganic salt to the water- and oil-repellent agent.

[0017] The organic salt is generally a metal salt of an organic acid.

[0018] Examples of the organic acid include a carboxylic acid having a—COOH group, a sulfonic acid having a —SO₃H group and a sulfatemonoester having a —OSO₃H group in molecule.

[0019] Examples of the carboxylic acid include formic acid, acetic acid,oxalic acid, phthalic acid, citric acid, propionic acid and butyricacid. Examples of the sulfonic acid include taurine, taurine derivatives(e.g., N-cocoylmethyltaurine) and alkylsulfonic acid (The carbon numberof an alkyl group may be, for example, from 1 to 30, particularly from 5to 20.)(e.g., tetradecenesulfonic acid). Examples of sulfate monoesterinclude monoalkyl sulfate (The carbon number of an alkyl group may be,for example, from 1 to 30, particularly from 5 to 20.),polyoxyalkylenealkylether sulfate (The carbon number of an oxyalkylenegroup may be 2 or 3, and the carbon number of an alkyl group may be, forexample, from 1 to 30, particularly from 5 to 20.). Specific examples ofthe sulfate monoester include lauryl sulfate andpolyoxyethylenelaurylether sulfate.

[0020] A metal in the metal salt of organic acid is a mono- totetra-valent, particularly mono- to tri-valent metal. Examples of themetal include an alkaline metal (e.g., potassium and sodium), analkaline earth metal (e.g., calcium) and aluminum.

[0021] The amount of the metal salt of organic acid is, for example,from 0.1 to 1,000 parts by weight, particularly from 10 to 500 parts byweight, per 1 part by weight (solid content) of the fluorine-containingcompound.

[0022] In the step (2) in the method of the present invention, pH of thetreatment liquid is brought to at most 7. pH of the treatment liquid ispreferably at most 3, more preferably at most 2. pH can be decreased byaddition of an acid such as an aqueous solution of citraconic acid andan aqueous solution of sulfamic acid to the treatment liquid.

[0023] In the step (3) of the method of the present invention, thetreatment liquid is applied to the textile. The water- and oil-repellentagent can be applied to a substrate to be treated (that is, the textile)by a know procedure. The application of the treatment liquid can beconducted by immersion, spraying and coating. Usually, the treatmentliquid is diluted with an organic solvent or water, and is adhered tosurfaces of the substrate by a well-known procedure such as an immersioncoating, a spray coating and a foam coating to a fabric (for example, acarpet cloth), a yarn (for example, a carpet yarn) or an original fiber.If necessary, the treatment liquid is applied together with a suitablecrosslinking agent, followed by curing. It is also possible to addmothproofing agents, softeners, antimicrobial agents, flame retardants,antistatic agents, paint fixing agents, crease-proofing agents, etc. tothe treatment liquid. The concentration of the water- and oil-repellentagent active component (that is, the fluorine-containing compound) inthe treatment liquid contacted with the substrate may be from 0.05 to10% by weight, based on the treatment liquid. A stain blocking agent mayused in the amount of, for example, 0 to 1,000 parts by weight,particularly 1 to 500 parts by weight, in terms of solid, per 100 partsby weight of the fluorine-containing compound.

[0024] In the step (4) of the method of the present invention, thetextile is thermally treated. The thermal treatment can be conducted byapplying a steam (for example, 90 to 110° C.) to the textile under anormal pressure for e.g., 10 seconds to 10 minutes.

[0025] In the step (5) of the method of the present invention, thetextile is washed with water and dehydrated. The thermally treatedtextile is washed with water at least once. Then, in order to removeexcess water, the textile is dehydrated by a usual dehydration proceduresuch as a centrifuging and vacuuming procedure.

[0026] After the step (5), the textile can be dried.

[0027] The fluorine-containing compound is a fluorine-containing polymerand/or a fluorine-containing low molecular weight compound.

[0028] The fluorine-containing polymer may be a polymer comprising arepeat unit derived from a fluoroalkyl group-containing monomer such asa fluoroalkyl group-containing (meth)acrylate, a fluoroalkylgroup-containing maleate or fumarate, or a fluoroalkyl group-containingurethane.

[0029] The fluoroalkyl group-containing (meth)acrylate ester may be ofthe formula:

Rf—A—OCOCR¹¹═CH₂

[0030] wherein Rf is a fluoroalkyl group having 3 to 21 carbon atoms,R¹¹ is a hydrogen atom or a methyl group, and A is a divalent organicgroup.

[0031] In the above formula, A may be a linear or branched alkylenegroup having 1 to 20 carbon atoms, a —SO₂N(R²¹)R²²— group or a—CH₂CH(OR²³)CH₂— group (R²¹ is an alkyl group having 1 to 10 carbonatoms, R²² is a linear or branched alkylene group having 1 to 10 carbonatoms, and R²³ is a hydrogen atom or an acyl group having 1 to 10 carbonatoms).

[0032] Examples of the fluoroalkyl group-containing (meth)acrylate areas follows:

 Rf—(CH₂)_(n)OCOCR³═CH₂  (2)

 Rf—O—Ar—CH₂OCOCR³═CH₂  (6)

[0033] wherein Rf is a fluoroalkyl group having 3 to 21 carbon atoms, R¹is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R² isan alkylene group having 1 to 10 carbon atoms, R³ is a hydrogen atom ora methyl group, and Ar is arylene group optionally having a substituent,and n is an integer of 1 to 10.

[0034] Specific examples of the fluoroalkyl group-containing(meth)acrylate are as follows:

[0035] CF₃(CF₂)₇(CH₂)₁₀OCOCH═CH₂

[0036] CF₃(CF₂)₇(CH₂)₁₀OCOC(CH₃)═CH₂

[0037] CF₃(CF₂)₆CH₂OCOCH═CH₂

[0038] CF₃(CF₂)₈CH₂OCOC(CH₃)═CH₂

[0039] (CF₃)₂CF(CF₂)₆(CH₂)₂OCOCH═CH₂

[0040] (CF₃)₂CF(CF₂)₈(CH₂)₂OCOCH═CH₂

[0041] (CF₃)₂CF(CF₂)₁₀(CH₂)₂OCOCH═CH₂

[0042] (CF₃)₂CF(CF₂)₆(CH₂)₂OCOC(CH₃)═CH₂

[0043] (CF₃)₂CF(CF₂)₈(CH₂)₂OCOC(CH₃)═CH₂

[0044] (CF₃)₂CF(CF₂)₁₀(CH₂)₂OCOC(CH₃)═CH₂

[0045] CF₃CF₂(CF₂)₆(CH₂)₂OCOCH═CH₂

[0046] CF₃CF₂(CF₂)₈(CH₂)₂OCOCH═CH₂

[0047] CF₃CF₂(CF₂)₁₀(CH₂)₂OCOCH═CH₂

[0048] CF₃CF₂(CF₂)₆(CH₂)₂OCOC(CH₃)═CH₂

[0049] CF₃CF₂(CF₂)₈(CH₂)₂OCOC(CH₃)═CH₂

[0050] CF₃CF₂(CF₂)₁₀(CH₂)₂OCOC (CH₃)═CH₂

[0051] CF₃(CF₂)₇SO₂N(CH₃)(CH₂)₂OCOCH═CH₂

[0052] CF₃(CF₂)₇SO₂N(C₂H₅)(CH₂)₂OCOCH═CH₂

[0053] (CF₃)₂CF(CF₂)₈CH₂CH(OCOCH₃)CH₂OCOC(CH₃)═CH₂

[0054] (CF₃)₂CF(CF₂)₆CH₂CH(OH)CH₂OCOCH═CH₂

[0055] A fluoroalkyl group-containing urethane monomer deriving thefluorine-containing polymer can be prepared by reacting:

[0056] (a) a compound having at least two isocyanate groups,

[0057] (b) a compound having one carbon-carbon double bond and at leastone hydroxyl group or amino group, and

[0058] (c) a fluorine-containing compound one hydroxyl group or aminogroup.

[0059] Examples of the compound (a) include the followings:

[0060] OCN(CH₂)₆NCO

[0061] The compound (a) is preferably a diisocyanate. However, atriisocyanate and a polyisocyanate can be also used for the reaction.

[0062] For example, a trimer of diisocyanate, polymeric MDI(diphenylmethane diisocyanate) and an adduct of diisocyanate with apolyhydric alcohol such as trimethylol propane, trimethylol ethane andglycerol can be also used for the reaction.

[0063] Examples of the triisocyanate and the polyisocyanate are asfollows:

[0064] The compound (b) may be, for example, a compound of each of theformulas:

[0065] CH₂═CH—CH₂—OH

[0066] CH₂═CH—CH₂—NH₂

[0067] In the formula, R¹ is a hydrogen atom or a methyl group. X is asfollows:

[0068] —(CH₂)_(p)OH

[0069] —(CH₂CH₂O)_(n)H

[0070] —(CH₂CH₂O)_(m)(CH₂CH₂CH₂CH₂O)_(n)H

[0071] —(CH₂CH₂CH₂CH₂O)_(m)(CH₂CH₂O)_(n)H

[0072] wherein m and n is a number of 1 to 300.

[0073] The compound (c) may be a compound of the formula:

R_(f)—R²—OH, or

R_(f)—R²—NH₂

[0074] wherein R_(f) is a fluoroalkyl group having 1 to 22 carbon atoms,and R² is an alkylene group having 1 to 10 carbon atoms and may have aheteroatom.

[0075] Examples of the compound (c) may be the followings:

[0076] CF₃CH₂ _(OH)

[0077] F(CF₂)₈CH₂CH₂OH

[0078] F(CF₂)₆(CH₂)₆OH

[0079] F(CF₂)₃CH₂NH₂

[0080] F(CF₂)₇CH₂NH₂

[0081] The compounds (a), (b) and (c) may be reacted such that when thecompound (a) is a diisocyanate, both the compounds (b) and (c) are inamounts of 1 mol based on 1 mol of the compound (a); when the compound(a) is a triisocyanate, the compound (b) is in an amount of 1 mol andthe compound (c) is in an amount of 2 mol based on 1 mol of the compound(a).

[0082] The fluorine-containing polymer constituting the water- andoil-repellent agent may comprise:

[0083] (I) a repeat unit derived from a monomer having a fluoroalkylgroup, and

[0084] (II) a repeat unit derived from a fluorine-free monomer.

[0085] The fluorine-containing polymer constituting the water- andoil-repellent agent may comprise:

[0086] (I) a repeat unit derived from a monomer having a fluoroalkylgroup,

[0087] (II) a repeat unit derived from a fluorine-free monomer, and

[0088] (III) a repeat unit derived from a crosslinkable monomer.

[0089] Examples of the monomer having fluoroalkyl group constituting therepeat unit (I) include the same as the above-mentioned fluoroalkylgroup-containing monomer such as a fluoroalkyl group-containing(meth)acrylate.

[0090] The repeat unit (II) is preferably derived from a fluorine-freeolefinically unsaturated monomer. Non-limiting examples of a preferablemonomer constituting the repeat unit (II) include, for example,ethylene, vinyl acetate, vinyl chloride such as vinyl chloride,vinylidene halide such as vinylidene chloride, acrylonitrile, styrene,polyethyleneglycol (meth)acrylate, polypropyleneglycol (meth)acrylate,methoxypolyethyleneglycol (meth)acrylate, methoxypolypropyleneglycol(meth)acrylate, vinyl alkyl ether and isoprene.

[0091] The monomer constituting the repeat unit (II) may be a(meth)acrylate ester having an alkyl group. The number of carbon atomsof the alkyl group may be from 1 to 30, for example, from 6 to 30, e.g.,from 10 to 30. For example, the monomer constituting the repeat unit(II) may be acrylates of the general formula:

CH₂═CA³COOA⁴

[0092] wherein A³ is a hydrogen atom or a methyl group, and A⁴ is analkyl group represented by C_(n)H_(2n+1) (n=1 to 30). Thecopolymerization with this monomer can optionally improve variousproperties such as water- and oil-repellency and soil releasability;cleaning durability, washing durability and abrasion resistance of saidrepellency and releasability; solubility in solvent; hardness; andfeeling.

[0093] The crosslinkable monomer constituting the repeat unit (III) maybe a fluorine-free vinyl monomer having at least two reactive groups.The crosslinkable monomer may be a compound having at least twocarbon-carbon double bonds, or a compound having at least onecarbon-carbon double bond and at least one reactive group.

[0094] Examples of the crosslinkable monomer includediacetoneacrylamide, (meth)acrylamide, N-methylolacrylamide,hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate,3-chloro-2-hydroxypropyl (meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, butadiene,chloroprene and glycidyl (meth)acrylate, to which the crosslinkablemonomer is not limited. The copolymerization with this monomer canoptionally improve various properties such as water-repellency and soilreleasability; cleaning durability and washing durability of saidrepellency and releasability; solubility in solvent; hardness; andfeeling.

[0095] The fluorine-containing polymer preferably has a weight averagemolecular weight of 2,000 to 1,000,000.

[0096] Preferably, the amount of the repeat unit (I) is from 40 to 90%by weight, more preferably from 50 to 80% by weight,

[0097] the amount of the repeat unit (II) is from 5 to 60% by weight,more preferably from 10 to 40% by weight, and the amount of the repeatunit (III) is from 0 to 10% by weight, more preferably 0.1 to 10% byweight, for example 0.5 to 10% by weight,

[0098] based on the fluorine-containing polymer.

[0099] The fluorine-containing polymer in the present invention can beproduced by any polymerization method, and the conditions of thepolymerization reaction can be arbitrary selected. The polymerizationmethod includes, for example, solution polymerization and emulsionpolymerization. Among them, the emulsion polymerization is particularlypreferred.

[0100] In the solution polymerization, there can be used a method ofdissolving the monomers in an organic solvent in the presence of apolymerization initiator, replacing the atmosphere by nitrogen, chargingvinyl chloride and/or vinylidene chloride (A-II) and stirring themixture with heating at the temperature within the range, for example,from 50° C. to 120° C. for 1 hour to 10 hours. Examples of thepolymerization initiator include azobisisobutyronitrile, benzoylperoxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide,t-butyl peroxypivalate and diisopropyl peroxydicarbonate. Thepolymerization initiator is used in the amount within the range from0.01 to 5 parts by weight based on 100 parts by weight of the monomers.

[0101] The organic solvent is inert to the monomer and dissolves them,and examples thereof include pentane, hexane, heptane, octane,cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran,1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate,butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane,trichloroethylene, perchloroethylene, tetrachlorodifluoroethane andtrichlorotrifluoroethane. The organic solvent may be used in the amountwithin the range from 50 to 1,000 parts by weight based on 100 parts byweight of whole of the monomers.

[0102] In the emulsion polymerization, there can be used a method ofemulsifying the monomers in water in the presence of a polymerizationinitiator and an emulsifying agent, replacing the atmosphere bynitrogen, charging vinyl chloride and/or vinylidene chloride (A-II) andcopolymerizing with stirring at the temperature within the range, forexample, from 50° C. to 80° C. for 1 hour to 10 hours. As thepolymerization initiator, for example, water-soluble initiators (e.g.,benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate,1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetylperoxide, azobisisobutylamidine dihydrochloride, azobisisobutyronitrile,sodium peroxide, potassium persulfate and ammonium persulfate) andoil-soluble initiators (e.g., azobisisobutyronitrile, benzoyl peroxide,di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butylperoxypivalate and diisopropyl peroxydicarbonate) are used. Thepolymerization initiator may be used in the amount within the range from0.01 to 5 parts by weight based on 100 parts by weight of the monomers.

[0103] In order to obtain a copolymer dispersion in water, which issuperior in storage stability, it is desirable that the monomers areatomized in water by using an emulsifying device capable of applying astrong shattering energy (e.g., a high-pressure homogenizer and anultrasonic homogenizer) and then polymerized with using the oil-solublepolymerization initiator. As the emulsifying agent, various emulsifyingagents such as an anionic emulsifying agent, a cationic emulsifyingagent and a nonionic emulsifying agent can be used in the amount withinthe range from 0.5 to 10 parts by weight based on 100 parts by weight ofthe monomers. When the monomers are not completely compatibilized, acompatibilizing agent capable of sufficiently compatibilizing them(e.g., a water-soluble organic solvent and a low-molecular weightmonomer) is preferably added to these monomers. By the addition of thecompatibilizing agent, the emulsifiability and copolymerizability can beimproved.

[0104] Examples of the water-soluble organic solvent include acetone,methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycolmonomethyl ether, dipropylene glycol, tripropylene glycol and ethanol.The water-soluble organic solvent may be used in the amount within therange from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight,based on 100 parts by weight of water.

[0105] The fluorine-containing low molecular weight compound may have amolecular weight of less than 2,000, for example, from 500 to 1,500 andmay be a fluoroalkyl group-containing compound.

[0106] The fluorine-containing low molecular weight compound may be, forexample, a fluoroalkyl group-containing urethane or a fluoroalkylgroup-containing ester.

[0107] The fluoroalkyl group-containing urethane can be prepared byreacting

[0108] (i) a compound having at least two isocyanate groups, with

[0109] (ii) a fluorine-containing compound having one hydroxyl group,amino group or epoxy group.

[0110] Examples of the compound having at least two isocyanate groups(i) are the same as those of the above-mentioned compound having atleast two isocyanate groups (a) used for the fluoroalkylgroup-containing urethane monomer deriving the fluorine-containingcopolymer.

[0111] Specific examples of the fluorine-containing compound having onehydroxyl group, amino group or epoxy group (ii) are as follows:

[0112] CF₃CF₂(CF₂CF₂)_(n)CH₂CH₂OH

[0113] CF₃CF₂(CF₂CF₂)_(n)CH₂CH₂NH₂

[0114] [n is from 2 to 8]

[0115] [n is from 2 to 8]

[0116] The fluoroalkyl group-containing ester can be prepared byreacting:

[0117] (iii) a polybasic carboxylic acid compound, with

[0118] (ii) a fluorine-containing compound having one hydroxyl group,amino group or epoxy group.

[0119] The polybasic carboxylic acid compound is a compound having atleast 2, preferably 2 to 4 carboxylic acid groups.

[0120] Specific examples of the polybasic carboxylic acid compound areas follows:

[0121] HOOC(CH₂)_(n)COOH

[0122] [n is 2, 4 or 6]

[0123] Examples of the fluorine-containing compound having one hydroxylgroup, amino group or epoxy group (ii) forming the fluoroalkylgroup-containing ester are the same as those of the above-mentionedfluorine-containing compound having one hydroxyl group, amino group orepoxy group (ii) forming the fluoroalkyl group-containing urethane.

[0124] The fluorine-containing compound may be the fluorine-containingpolymer, the fluorine-containing low molecular weight compound, or amixture of the fluorine-containing polymer and the fluorine-containinglow molecular weight compound.

[0125] The amount of the fluorine-containing compound is at most 60% byweight, preferably from 1 to 40% by weight, for example, 1 to 30% byweight, based on the water- and oil-repellent agent. The amount of theemulsifier may be from 0.5 to 15 parts by weight, based on 100 parts byweight of the fluorine-containing compound.

[0126] The substrate to be treated in the present invention ispreferably a textile, particularly a carpet. The textile includesvarious examples. Examples of the textile include animal- orvegetable-origin natural fibers such as cotton, hemp, wool and silk;synthetic fibers such as polyamide, polyester, polyvinyl alcohol,polyacrylonitrile, polyvinyl chloride and polypropylene; semisyntheticfibers such as rayon and acetate; inorganic fibers such as glass fiber,carbon fiber and asbestos fiber; and a mixture of these fibers. Themethod of the present invention can be suitably used in carpets made ofnylon fibers, polypropylene fibers and/or polyester fibers, because thepresent invention provides excellent resistance to a detergent solutionand brushing (mechanical).

[0127] The textile may be in any form such as a fiber and a fabric. Whenthe carpet is treated according to the method of the present invention,the carpet may be formed after the fibers or yarns are treated accordingto the present invention, or the formed carpet may be treated accordingto the present invention. The water- and oil-repellent agent can be usedin the state that the fluorine-containing compound is diluted to thecontent of 0.02 to 30% by weight, preferably 0.02 to 10% by weight.

PREFERRED EMBODIMENTS OF THE INVENTION

[0128] The following Examples further illustrate the present inventionbut are not to be construed to limit the scope thereof. The waterrepellency and oil repellency of the carpets obtained in the Examplesand Comparative Example were evaluated.

[0129] Test procedures of the water repellency and the oil repellencyare as follows.

[0130] (1) Water Repellency

[0131] A droplet of a isopropyl alcohol (IPA)/water mixture liquid shownin Table 1 is softly positioned on a carpet surface, and a maximumcontent of IPA (% by volume) in the liquid which maintains the dropletshape is taken as the result of the water repellency.

[0132] Specific procedure is as follows.

[0133] A carpet treated for giving repellency is stored in athermo-hygrostat having a temperature of 21° C. and a humidity of 65%for at least 4 hours. A test liquid (having the composition shown inTable 1) has been also stored at 21° C. The temperature of a measurementroom is controlled to be about 21° C. Droplets of the test liquid in anamount of 50 μL are softly dropped by a micropipette on the carpet andthe diameter of the droplets is 5 mm. The micropippete is verticallystood and droplets are softly dropped. Five droplets are positioned. If4 or 5 droplets remain on the carpet after standing for 10 seconds, itis evaluated that the test liquid passes the test. The maximum contentof IPA (% by volume) in the test liquid which passes the test is takenas the result of the water repellency. TABLE 1 Mixing composition (% byvolume) Isopropyl alcohol Water 100 0 90 10 80 20 70 30 60 40 50 50 4060 30 70 25 75 20 80 15 85 10 90  5 95  2 98  0 100 Fail Inferior to IPA0%/water 100%

[0134] (2) Oil Repellency

[0135] The oil repellency is evaluated as follows.

[0136] A carpet treated for giving repellency is stored in athermo-hygrostat having a temperature of 21° C. and a humidity of 65%for at least 4 hours. A test liquid (having the composition shown inTable 2) has been also stored at 21° C. The temperature of a measurementroom is controlled to be about 21° C. Droplets of the test liquid in anamount of 50 μL are softly dropped by a micropipette on the carpet andthe diameter of the droplets is 5 mm. The micropippete is verticallystood and droplets are softly dropped. Five droplets are positioned. If4 or 5 droplets remain on the carpet after standing for 10 seconds, itis evaluated that the test liquid passes the test. The maximum point ofthe test liquid which passes the test is taken as the result of the oilrepellency. TABLE 2 Oil Surface tension repellency Test solution(dyne/cm, 25° C.) 8 n-Heptane 20.0 7 n-Octane 21.8 6 n-Decane 23.5 5n-Dodecane 25.0 4 n-Tetradecane 26.7 3 n-Hexadecane 27.3 2 Mixturesolution 29.6 of n-hexadecane 35/Nujol 65 1 Nujol 31.2 0 Inferior to 1 —

PREPARATIVE EXAMPLE 1

[0137] 200 g of perfluoroalkyl acrylate: CH₂═CH—COOCH₂CH₂—Rf (a mixturewherein a molar ratio of Rf=C₆F₁₃, C₈F₁₇, C₁₀F₂₁, C₁₂F₂₅ and C₁₄F₂₉ was2:40:30:15:3, an average molecular weight of 528) and 15 g of stearylacrylate were sufficiently mixed, and then 20 g ofpolyoxyethylene(n=15)octylphenyl ether (a nonionic emulsifier), 10 g ofsodium lauryl sulfate (an anionic emulsifier), 0.15 g of laurylmercaptan, 70 g of tripropylene glycol and 450 g of deionized water wereadded and the mixture was emulsified by a high pressure homogenizer. Theresultant emulsion was charged into a 1 L autoclave, and the atmospherein the autoclave was replaced with nitrogen. 70 g of vinyl chloride wasinjected and a solution of an initiator, ammonium persulfate (1.5 g) inwater (10 g) was added. The temperature was increased to 60° C. toinitiate the polymerization. The mixture was stirred at 60° C. for 6hours to give an aqueous emulsion of a copolymer. The composition ofmonomers in the resultant copolymer was almost the same as the chargedmonomer composition.

COMPARATIVE EXAMPLE 1

[0138] 0.4 g of the emulsion prepared in Preparative Example 1 and 5 gof a stain blocking agent (FX-657, manufactured by 3M) were diluted withwater to give the total amount of 1,000 g. A 10% aqueous sulfamic acidsolution was added to the emulsion so that pH of the emulsion was 1.5,to give a treatment liquid.

[0139] A carpet (8.9 cm×18.2 cm, nylon-6, cut pile, density: 36 oz/yd²)was immersed in this treatment liquid for 30 seconds and squeezed tohave a WPU (wet pick up) amount of 300%. Then, a normal-pressure steamertreatment (temperature: 100° C. to 107° C.) was conducted for 90 secondsunder the state that a pile surface was upside. The carpet was lightlyrinsed with 2 L of water and then centrifugal dehydration was conductedto give a WPU amount of 25%. Finally, the carpet was thermally cured at110° C. for 10 minutes. Then, the evaluation of water repellency and oilrepellency was conducted. The results are shown in Table A.

COMPARATIVE EXAMPLE 2

[0140] 0.4 g of the emulsion prepared in Preparative Example 1, 5 g of astain blocking agent (FX-657, manufactured by 3M) and a metal salt,MgSO₄ (OWG (on the weight of goods) was 1, 2, 4 and 8) were diluted withwater to give the total amount of 1,000 g. A 10% aqueous sulfamic acidsolution was added to the emulsion so that pH of the emulsion was 1.5,to give a treatment liquid (The normalities of the treatment liquidswere 0.055 N, 0.11 N, 0.22 N and 0.44 N, respectively.).

[0141] A carpet (8.9 cm×18.2 cm, nylon-6, cut pile, density: 36 oz/yd²)was immersed in this treatment liquid for 30 seconds and squeezed tohave a WPU (wet pick up) amount of 300%. Then, a normal-pressure steamertreatment (temperature: 100° C. to 107° C.) was conducted for 90 secondsunder the state that a pile surface was upside. The carpet was lightlyrinsed with 2 L of water and then centrifugal dehydration was conductedto give a WPU amount of 25%. Finally, the carpet was thermally cured at110° C. for 10 minutes. Then, the evaluation of water repellency and oilrepellency was conducted. The results are shown in Table A.

EXAMPLES 1 TO 3

[0142] 0.4 g of the emulsion prepared in Preparative Example 1, 5 g of astain blocking agent (FX-657, manufactured by 3M) and an organic saltshown in Table A (Example 1: potassium formate, Example 2: potassiumoxalate, Example 3: potassium phthalate) (added so that a resultanttreatment liquid had the normality of 0.055 N, 0.11 N, 0.22 N or 0.44 N)were diluted with water to give the total amount of 1,000 g. A 10%aqueous sulfamic acid solution was added to the emulsion so that pH ofthe emulsion was 1.5, to give a treatment liquid.

[0143] A carpet (8.9 cm×18.2 cm, nylon-6, cut pile, density: 36 oz/yd²)was immersed in this treatment liquid for 30 seconds and squeezed tohave a WPU (wet pick up) amount of 300%. Then, a normal-pressure steamertreatment (temperature: 100° C. to 107° C.) was conducted for 90 secondsunder the state that a pile surface was upside. The carpet was lightlyrinsed with 2 L of water and then centrifugal dehydration was conductedto give a WPU amount of 25%. Finally, the carpet was thermally cured at110° C. for 10 minutes. Then, the evaluation of water repellency and oilrepellency was conducted. The results are shown in Table A. TABLE AFluorine- Stain Normal- Water Oil containing blocking ity repel- repel-polymer agent Salt added (N) lency lency Com. Ex. 1 Pre. Ex. 1 FX-657 Noaddition — 25 0 Com. Ex. 2 Pre. Ex. 1 FX-657 MgSO₄ 0.055 25 1 (OWG = 1)Pre. Ex. 1 FX-657 MgSO₄ 0.11 20 1 (OWG = 2) Pre. Ex. 1 FX-657 MgSO₄ 0.2225 2 (OWG = 4) Pre. Ex. 1 FX-657 MgSO₄ 0.44 30 2 (OWG = 8) Ex. 1 Pre.Ex. 1 FX-657 Potassium 0.055 25 2 formate Pre. Ex. 1 FX-657 Potassium0.11 30 2 formate Pre. Ex. 1 FX-657 Potassium 0.22 90 4 formate Pre. Ex.1 FX-657 Potassium 0.44 80 5 formate Ex. 2 Pre. Ex. 1 FX-657 Potassium0.055 25 1 oxalate Pre. Ex. 1 FX-657 Potassium 0.11 30 1 oxalate Pre.Ex. 1 FX-657 Potassium 0.22 80 4 oxalate Pre. Ex. 1 FX-657 Potassium0.44 80 5 oxalate Ex. 3 Pre. Ex. 1 FX-657 Potassium 0.055 25 1 phthalatePre. Ex. 1 FX-657 Potassium 0.11 25 1 phthalate Pre. Ex. 1 FX-657Potassium 0.22 40 3 phthalate Pre. Ex. 1 FX-657 Potassium 0.44 40 3phthalate

COMPARATIVE EXAMPLE 3

[0144] 0.4 g of the emulsion prepared in Preparative Example 1 and 5 gof a stain blocking agent (FX-657, manufactured by 3M) were diluted withwater to give the total amount of 1,000 g. A 10% aqueous sulfamic acidsolution was added to the emulsion so that pH of the emulsion was 2.6,to give a treatment liquid. A carpet B (8.9 cm×18.2 cm, nylon-6, cutpile, density: 32 oz/yd²) was immersed in this treatment liquid for 30seconds and squeezed to have a WPU (wet pick up) amount of 300%. Then, anormal-pressure steamer treatment (temperature: 100° C. to 107° C.) wasconducted for 90 seconds under the state that a pile surface was upside.The carpet was lightly rinsed with 2 L of water and then centrifugaldehydration was conducted to give a WPU amount of 25%. Finally, thecarpet was thermally cured at 110° C. for 10 minutes. Then, theevaluation of water repellency and oil repellency was conducted. Theresults are shown in Table B.

EXAMPLE 4

[0145] 0.4 g of the emulsion prepared in Preparative Example 1, 5 g of astain blocking agent (FX-657, manufactured by 3M) and sodium acetate(added so that a resultant treatment liquid had the normality of 0.012N, 0.031 N, 0.061 N, 0.091 N or 0.122 N) were diluted with water to givethe total amount of 1,000 g. A 10% aqueous sulfamic acid solution wasadded to the emulsion so that pH of the emulsion was 2.6, to give atreatment liquid. The carpet B was treated with the treatment liquid inthe same manner as in Comparative Example 3. The evaluation of waterrepellency and oil repellency was conducted. The results are shown inTable B.

EXAMPLE 5

[0146] 0.4 g of the emulsion prepared in Preparative Example 1, 5 g of astain blocking agent (FX-657, manufactured by 3M) and sodium formate(added so that a resultant treatment liquid has the normality of 0.0147N) were diluted with water to give the total amount of 1,000 g. A 10%aqueous sulfamic acid solution was added to the emulsion so that pH ofthe emulsion was 2.6, to give a treatment liquid. The carpet B wastreated with the treatment liquid in the same manner as in ComparativeExample 3. The evaluation of water repellency and oil repellency wasconducted. The results are shown in Table B. TABLE B Fluorine- StainWater Oil containing blocking Added Normality repel- repel- polymeragent salt (N) lency lency Com. Ex. 3 Pre. Ex. 1 FX-657 0 0 Fail 0 Ex. 4Pre. Ex. 1 FX-657 Sodium 0.012 70 4 acetate 0.031 70 4 0.061 70 5 0.09180 5 0.122 80 5 Ex. 5 Pre. Ex. 1 FX-657 Sodium 0.147 80 5 formate

EFFECT OF THE INVENTION

[0147] The present invention imparts excellent water-repellency andoil-repellency to a textile.

1. A method of preparing a treated textile, comprising steps of: (1)preparing a treatment liquid comprising a water- and oil-repellentagent, (2) adjusting pH of the treatment liquid to at most 7, (3)applying the treatment liquid to a textile, (4) treating the textilewith steam, and (5) washing the textile with water and dehydrating thetextile, wherein the water- and oil-repellent agent comprises at leastone fluorine-containing compound selected from the group consisting of afluorine-containing polymer and a fluorine-containing low molecularweight compound, and the water- and oil-repellent agent or the treatmentliquid contains an organic salt.
 2. The method according to claim 1,wherein the organic salt is a metal salt of an organic acid.
 3. Themethod according to claim 2, wherein the organic acid is a carboxylicacid, a sulfonic acid or a sulfate monoester.
 4. The method according toclaim 2, wherein the metal in the metal salt of organic acid is a mono-to tetra-valent metal.
 5. The method according to claim 1, wherein thefluorine-containing polymer comprises: (I) a repeat unit derived from amonomer having a fluoroalkyl group.
 6. The method according to claim 1,wherein the fluorine-containing polymer which comprises: (I) a repeatunit derived from a monomer having a fluoroalkyl group, and (II) arepeat unit derived from a fluorine-free monomer, and/or (III) a repeatunit derived from a crosslinkable monomer.
 7. The method according toclaim 1, wherein pH of the treatment liquid is brought to at most 3 inthe step (2).
 8. A textile obtainable by the method according toclaim
 1. 9. A carpet obtainable by the method according to claim
 1. 10.The carpet according to claim 9, wherein the carpet comprises a nylonfiber, a polypropylene fiber and/or a polyester fiber.
 11. A water- andoil-repellent agent usable in a method of treating a textile, comprisingsteps of: (1) preparing a treatment liquid comprising a water- andoil-repellent agent, (2) adjusting pH of the treatment liquid to at most7, (3) applying the treatment liquid to a textile, (4) treating thetextile with steam, and (5) washing the textile with water anddehydrating the textile, wherein the water- and oil-repellent agentcomprises at least one fluorine-containing compound selected from thegroup consisting of a fluorine-containing polymer and afluorine-containing low molecular weight compound, and the water- andoil-repellent agent or the treatment liquid contains an organic salt.